In 1975, Hamberg et al discovered an unstable intermediate in the conversion of prostaglandin G.sub.2 into the hemiacetal derivative in platelets [Proc. Nat. Acad. Sci. U.S.A., Vol 72, No. 8 page 2994 (1975)]. The intermediates have been named as thromboxane A.sub.2 and its structure has been proposed as follows: ##STR3##
TXA.sub.2 has been found to show various biological activities such as platelet aggregation, aorta contraction and thrombi formation and therefore is considered to be one of the cause by which diseases such as inflammation, thrombus and cardiac infarction are induced.
Some TXA.sub.2 analogues are proposed as compounds having antagonistic activity on TXA.sub.2 ; for example, compounds which replaced the oxygen atoms on 11a- and 9,11-epoxy-position of TXA.sub.2 by carbon atoms [see Japanese Patent Kokai No. 55-143930], and compounds having pinane skelton [Proc. Nat. Acad. Sci. U.S.A. Vol. 76, No. 6, page 2566 (1979)].
Recently, Hamanaka et al have proposed a series of 13-aza-TXA.sub.2 analogues which replaced the 13-position carbon atom by a nitrogen atom, [see Japanese Patent Kokai Nos. 57-108046, 57-24338, 58-13548 and 58-13551; i.e. European Patent No. 0044711 or U.S. Pat. No. 4,389,413.] of the general formula: ##STR4## [wherein A represents
(i) --CH.sub.2 CH.sub.2 --(CH.sub.2).sub.m --, PA1 (ii) cis--CH.dbd.CH--(CH.sub.2).sub.m --, PA1 (iii) --CH.sub.2 --O--(CH.sub.2).sub.m --, or ##STR5## (wherein m represents an integer of from 1 to 6, double bond in the formula (iv) represents E, Z or EZ, and a phenylene group represents o-, m- or p-phenylene group.); PA1 (i) an alkyl, alkoxy or alkylthio group of from 1 to 8 carbon atom(s), PA1 (ii) a cycloalkyl or cycloalkyloxy group of from 4 to 7 carbon atoms unsubstituted or substituted by at least one of straight or branched alkyl group of from 1 to 8 carbon atom(s), or PA1 (iii) a group of general formula: ##STR6## (wherein Z represents a bond, a oxygen atom or sulphur atom, and R.sup.60 represents a hydrogen atom, a halogen atom, a hydroxy group, a straight or branched alkyl or alkoxy group of from 1 to 5 carbon atom(s), a triharomethyl, an amino group or a monoalkylamino or dialkylamino group of from 1 to 5 carbon atom(s)); PA1 (i) a group of general formula: --CH.sub.2 CH.sub.2 --(CH.sub.2).sub.m --, PA1 (ii) a group of general formula: cis--CH.dbd.CH--(CH.sub.2).sub.m --, PA1 (iii) a group of general formula: --CH.sub.2 O--(CH.sub.2).sub.m --, PA1 (iv) a group of general formula: --S--(CH.sub.2).sub.m -- (wherein m represents an integer of from 1 to 6.) or PA1 (v) a group of general formula: ##STR8## R.sup.1 represents a hydrogen atom or a straight or branched alkyl group of from 1 to 12 carbon atom(s); PA1 (i) a phenyl, phenoxy or phenylthio group unsubstituted or substituted by at least one of straight or branched alkyl or alkoxy group of from 1 to 6 carbon atom(s), halogen atom or hydroxy group, PA1 (ii) a straight or branched alkyl, alkenyl or alkynyl group of from 1 to 6 carbon atom(s) unsubstituted or substituted by at least one of halogen atom or hydroxy group, PA1 (iii) a cycloalkyl, cycloalkyloxy or cycloalkylthio group of from 4 to 7 carbon atoms unsubstituted or substituted by at least one of straight or branched alkyl group of from 1 to 6 carbon atom(s), halogen atom or hydroxy group, PA1 (iv) a naphthyl, indolyl or indanyl group, or PA1 (v) an amino group unsubstituted or substituted by at least one of straight or branched alkyl group of from 1 to 6 carbon atom(s); and PA1 (1) by the method using a diazoalkane PA1 (2) by the method using an alkyl halide PA1 (3) by the method using DMF-alkylacetal and PA1 (4) by the method reacting with a corresponding alkanol
R.sup.10 represents a hydrogen atom or a straight or branched alkyl group of from 1 to 12 carbon atom(s); PA0 Each of R.sup.20 represent hydrogen atoms or methyl groups; PA0 R.sup.30 represents a hydroxy group or a hydrogen atom; PA0 R.sup.40 represents a bond or a straight or branched alkylene group of from 1 to 5 carbon atom(s); and PA0 R.sup.50 represents PA0 And the wavy line ( ) attached to 15-position carbon atom represents .alpha.- or .beta.-configuration (i.e. S- or R-configuration), or mixture (i.e. RS) thereof. PA0 R.sup.2 represents a bond or a straight or branched alkylene or alkenylene group of from 1 to 10 carbon atom(s) unsubstituted or substituted by at least one of hydroxy group, amino group, halogen atom or phenylthio group; PA0 R.sup.3 represents PA0 R.sup.4 represents a hydrogen atom or a methyl group. PA0 (A) by the method with using mixed acid anhydride PA0 (B) by the method with using acid halide PA0 (C) by the method with using DCC (dicyclohexylcarbodiimide) etc. PA0 R.sup.6 --tetrahydropyran-2-yl group, tetrahydrofuran-2-yl group or 1-ethoxyethyl group PA0 R.sup.7 --phenyl group unsubstituted or substituted by straight or branched alkyl group of from 1 to 4 carbon atom(s) or an alkyl or alkoxy group of from 1 to 6 carbon atom(s) PA0 T.sup.1 --p-toluenesulphonyl group or methanesulphonyl group PA0 D--a group of general formula: --(CH.sub.2).sub.m -- or general formula: ##STR14## X.sup.1 --a halogen atom B.sup.1 --a group of (i) general formula: cis--CH.dbd.CH--(CH.sub.2).sub.m --, or (ii) general formula: ##STR15## B.sup.2 --a group of general formula: --CH.sub.2 --CH.sub.2 --(CH.sub.2).sub.m -- ##STR16## PA0 R.sup.2b --a bond, a straight or branched alkylene or alkenylene group unsubstituted or substituted by at least one of protected hydroxy group (e.g. tetrahydropyran-2-yloxy group, tetrahydrofuran-2-yloxy group or 1-ethoxyethyl group), protected amino group (e.g. benzyloxycarbonylamino group), halogen atom or phenylthio group. PA0 R.sup.9 --tetrahydropyran-2-yl group, tetrahydrofuran-2-yl group or 1-ethoxyethyl group. ##STR25## PA0 (1) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-phenyl-17,18,19,20-tet ranor-11a-carbathromb-5Z-enoic acid, PA0 (2) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-(4-methylphenyl)-17,18 ,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (3) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-(4-propylphenyl)-17,18 ,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (4) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-(4-butylphenyl)-17,18, 19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (5) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-(4-methoxyphenyl)-17,1 8,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (6) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-(3-chlorophenyl)-17,18 ,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (7) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo- 17-phenyl-18,19,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (8) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-17-(4-methylphenyl)-18,19 ,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (9) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-17-(4-propylphenyl)-18,19 ,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (10) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-17-(4-butylphenyl)-18,19, 20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (11) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-17-(4-methoxyphenyl)-18,1 9,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (12) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-17-(3-chlorophenyl)-18,19 ,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (13)9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-18-phenyl-19,20-dinor- 11a-carbathromb-5Z-enoic acid, PA0 (14) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-18-(4-methylphenyl)-19,20 -dinor-11a-carbathromb-5Z-enoic acid, PA0 (15) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-18-(4-propylphenyl)-19,20 -dinor-11a-carbathromb-5Z-enoic acid, PA0 (16) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-18-(4-butylphenyl)-19,20- dinor- 11a-carbathromb-5Z-enoic acid, PA0 (17) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-18-(4-methoxyphenyl)-19,2 0-dinor-11a-carbathromb-5Z-enoic acid, PA0 (18) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-18-(4-chlorophenyl)-19,20 -dinor-11a-carbathromb-5Z-enoic acid, PA0 (19) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-methyl-16-phenyl-17,18 ,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (20) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-methyl-16-(4-methylphe nyl)-17,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (21) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-methyl-16-(4-propylphe nyl)-17,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (22) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-methyl-16-(4-butylphen yl)-17,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (23) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-methyl-16-(4-methoxyph enyl)-17,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (24) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-methyl-16-(3-chlorophe nyl)-17,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (25) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-methyl-17-phenyl-18,19 ,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (26) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo16-methyl-17-(4-methylphen yl)-18,19,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (27) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-methyl-17-(4-propylphe nyl)-18,19,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (28) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-methyl-17-(4-butylphen yl)-18,19,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (29) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-methyl-17-(4-methoxyph enyl)-18,19,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (30) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-methyl-17-(3-chlorophe nyl)-18,19,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (31) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-methyl-18-phenyl-19,20 -dinor-11a-carbathromb-5Z-enoic acid, PA0 (32) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-methyl-18-(4-methylphe nyl)-19,20-dinor-11a-carbathromb-5Z-enoic acid, PA0 (33) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-methyl-18-(4-propylphe nyl)-19,20-dinor-11a-carbathromb-5Z-enoic acid, PA0 (34) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-methyl-18-(4-butylphen yl)-19,20-dinor-11a-carbathromb-5Z-enoic acid, PA0 (35) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo- 16-methyl-18-(4-methoxyphenyl)-19,20-dinor-11a-carbathromb-5Z-enoic acid, PA0 (36) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-methyl-18-(3-chlorophe nyl)-19,20-dinor-11a-carbathromb-5Z-enoic acid, PA0 (37) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15,15-dimethyl-16-phenyl- 17,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (38) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15,15-dimethyl-16-(4-meth ylphenyl)-17,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (39) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-(4-propylphenyl)-17,18 ,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (40) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-(4-butylphenyl)-17,18, 19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (41) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-(4-methoxyphenyl)-17,1 8,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (42) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-(3-chlorophenyl)-17,18 ,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (43) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15,15-dimethyl-17-phenyl- 18,19,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (44) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15,15-dimethyl-17-(4-meth ylphenyl)-18,19,20-trinor- 11a-carbathromb-5Z-enoic acid, PA0 (45) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15,15-dimethyl-17-(4-prop ylphenyl)-18,19,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (46) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15,15-dimethyl-17-(4-buty lphenyl)-18,19,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (47) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15,15-dimethyl-17-(4-meth oxyphenyl)-18,19,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (48) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15,15-dimethyl-17-(3-chlo rophenyl)-18,19,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (49) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15,15-dimethyl-18-phenyl- 19,20-dinor-11a-carbathromb-5Z-enoic acid, PA0 (50) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15,15-dimethyl-18-(4-meth ylphenyl)-19,20-dinor-11a-carbathromb-5Z-enoic acid, PA0 (51) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15,15-dimethyl-18-(4-prop ylphenyl)-19,20-dinor-11a-carbathromb-5Z-enoic acid, PA0 (52) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15,15-dimethyl-18-(4-buty lphenyl)-19,20-dinor-11a-carbathromb-5Z-enoic acid, PA0 (53) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15,15-dimethyl-18-(4-meth oxyphenyl)-19,20-dinor-11a-carbathromb-5Z-enoic acid, PA0 (54) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15,15-dimethyl-18-(3-chlo rophenyl)-19,20-dinor-11a-carbathromb-5Z-enoic acid, PA0 (55) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15,15-dimethyl-19-phenyl- 20-nor-11a-carbathromb-5Z-enoic acid, PA0 (56) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15,15-dimethyl-19-(4-meth ylphenyl)-20-nor-11a-carbathromb-5Z-enoic acid, PA0 (57) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15,15-dimethyl-19-(4-prop ylphenyl)-20-nor-11a-carbathromb-5Z-enoic acid, PA0 (58) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15,15-dimethyl-19-(4-buty lphenyl)-20-nor-11a-carbathromb-5Z-enoic acid, PA0 (59) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15,15-dimethyl-19-(4-meth oxyphenyl)-20-nor-11a-carbathromb-5Z-enoic acid, PA0 (60) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15,15-dimethyl-19-(3-chlo rophenyl)-20-nor-11a-carbathromb-5Z-enoic acid, PA0 (61) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16,16-dimethyl-17-phenyl- 18,19,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (62) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16,16-dimethyl-17-(4-meth ylphenyl)-18,19,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (63) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo- 16,16-dimethyl-17-(4-propylphenyl)-18,19,20-trinor-11a-carbathromb-5Z-enoi c acid, PA0 (64) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16,16-dimethyl-17-(4-buty lphenyl)-18,19,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (65) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16,16-dimethyl-17-(4-meth oxyphenyl)-18,19,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (66) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16,16-dimethyl-17-(3-chlo rophenyl)-18,19,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (67) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-methyl-16-phenyl-17,18 ,19,20-tetranor-11a-carbathromb-5Z,15E-dienoic acid, PA0 (68) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-methyl-16-(4-methylphe nyl)-17,18,19,20-tetranor-11a-carbathromb-5Z,15E-dienoic acid, PA0 (69) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-methyl-16-(4-propylphe nyl)-17,18,19,20-tetranor-11a-carbathromb-5Z,15E-dienoic acid, PA0 (70) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-methyl-16-(4-butylphen yl)-17,18,19,20-tetranor-11a-carbathromb-5Z,15E-dienoic acid, PA0 (71) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-methyl-16-(4-methoxyph enyl)-17,18,19,20-tetranor-11a-carbathromb-5Z,15E-dienoic acid, PA0 (72) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-methyl-16-(3-chlorophe nyl)-17,18,19,20-tetranor- 11a-carbathromb-5Z,15E-dienoic acid, PA0 (73) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-17-phenyl-18,19,20-trinor -11a-carbathromb-5Z,16E-dienoic acid, PA0 (74) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-17-(4-methylphenyl)-18,19 ,20-trinor-11a-carbathromb-5Z,16E-dienoic acid, PA0 (75) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-17-(4-propylphenyl)-18,19 ,20-trinor-11a-carbathromb-5Z,16E-dienoic acid, PA0 (76) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-17-(4-butylphenyl)-18,19, 20-trinor-11a-carbathromb-5Z,16E-dienoic acid, PA0 (77) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-17-(4-methoxyphenyl)-18,1 9,20-trinor-11a-carbathromb-5Z,16E-dienoic acid, PA0 (78) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-17-(3-chlorophenyl)-18,19 ,20-trinor-11a-carbathromb-5Z,16E-dienoic acid, PA0 (79) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-phenoxy-16,17,18,19,20 -pentanor-11a-carbathromb-5Z-enoic acid, PA0 (80) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-(4-methylphenoxy)-16,1 7,18,19,20-pentanor-11a-carbathromb-5Z-enoic acid, PA0 (81) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-(4-propylphenoxy)-16,1 7,18,19,20-pentanor-11a-carbathromb-5Z-enoic acid, PA0 (82) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-(4-butylphenoxy)-16,17 ,18,19,20-pentanor-11a-carbathromb-5Z-enoic acid, PA0 (83) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-(4-methoxyphenoxy)-16, 17,18,19,20-pentanor-11a-carbathromb-5Z-enoic acid, PA0 (84) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-(3-chlorophenoxy)-16,1 7,18,19,20-pentanor-11a-carbathromb-5Z-enoic acid, PA0 (85) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-phenylthio-16,17,18,19 ,20-pentanor-11a-carbathromb-5Z-enoic acid, PA0 (86) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-(4-methylphenylthio)-1 6,17,18,19,20-pentanor-11a-carbathromb-5Z-enoic acid, PA0 (87) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-(4-propylphenylthio)-1 6,17,18,19,20-pentanor-11a-carbathromb-5Z-enoic acid, PA0 (88) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-(4-butylphenylthio)-16 ,17,18,19,20-pentanor-11a-carbathromb-5Z-enoic acid, PA0 (89) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-(4-methoxyphenylthio)- 16,17,18,19,20-pentanor-11a-carbathromb-5Z-enoic acid, PA0 (90) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-(3-chlorophenylthio)-1 6,17,18,19,20-pentanor-11a-carbathromb-5Z-enoic acid, PA0 (91) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo- 16-phenylthio-17,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (92) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-(4-methylphenylthio)-1 7,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (93) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-(4-propylphenylthio)-1 7,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (94) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-(4-butylphenylthio)-17 ,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (95) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-(4-methoxyphenylthio)- 17,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (96) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-(3-chlorophenylthio)-1 7,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (97) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16,17,18,19,20-pentanor-1 1a-carbathromb-5Z-enoic acid, PA0 (98) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-17,18,19,20-tetranor-11a- carbathromb-5Z-enoic acid, PA0 (99) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-18,19,20-trinor-11a-carba thromb-5Z-enoic acid, PA0 (100) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-19,20-dinor- 11a-carbathromb-5Z-enoic acid, PA0 (101) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-20-nor-11a-carbathromb-5Z -enoic acid, PA0 (102) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-11a-carbathromb-5Z-enoic acid, PA0 (103) 90.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-20-methyl-11a-carbathrom b-5Z-enoic acid, PA0 (104) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-chloro-16,17,18,19,20- pentanor-11a-carbathromb-5Z-enoic acid, PA0 (105) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-chloro-17,18,19,20-tet ranor-11a-carbathromb-5Z-enoic acid, PA0 (106) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-17-chloro-18,19,20-trinor -11a-carbathromb-5Z-enoic acid, PA0 (107) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-18-chloro-19,20-dinor-11a -carbathromb-5Z-enoic acid, PA0 (108) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-19-chloro-20-nor-11a-carb athromb-5Z-enoic acid, PA0 (109) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-20-chloro-11a-carbathromb -5Z-enoic acid, PA0 (110) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo- 15-methyl-17,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (111) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-methyl-18,19,20-trinor -11a-carbathromb-5Z-enoic acid, PA0 (112) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-methyl-18,19,20-trinor -11a-carbathromb-5Z-enoic acid, PA0 (113) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-17-methyl-19,20-dinor-11a -carbathromb-5Z-enoic acid, PA0 (114) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-methyl-19,20-dinor-11a -carbathromb-5Z-enoic acid, PA0 (115) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-methyl-19,20-dinor-11a -carbathromb-5Z-enoic acid, PA0 (116) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-18-methyl-20-nor-11a-carb athromb-5Z-enoic acid, PA0 (117) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-17-methyl-20-nor-11a-carb athromb-5Z-enoic acid, PA0 (118) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-methyl-20-nor-11a-carb athromb-5Z-enoic acid, PA0 (119) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-methyl-20-nor- 11a-carbathromb-5Z-enoic acid, PA0 (120) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-19-methyl-11a-carbathromb -5Z-enoic acid, PA0 (121) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-18-methyl-11a-carbathromb -5Z-enoic acid, PA0 (122) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-17-methyl-11a-carbathromb -5Z-enoic acid, PA0 (123) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-methyl-11a-carbathromb -5Z-enoic acid, PA0 (124) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-methyl-11a-carbathromb -5Z-enoic acid, PA0 (125) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15,16-dimethyl-18,19,20-t rinor-11a-carbathromb-5Z-enoic acid, PA0 (126) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15,16-dimethyl-19,20-dino r-11a-carbathromb-5Z-enoic acid, PA0 (127) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15,17-dimethyl-19,20-dino r-11a-carbathromb-5Z-enoic acid, PA0 (128) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16,17-dimethyl-19,20-dino r-11a-carbathromb-5Z-enoic acid, PA0 (129) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15,16-dimethyl-20-nor-11a -carbathromb-5Z-enoic acid, PA0 (130) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15,17-dimethyl-20-nor-11a -carbathromb-5Z-enoic acid, PA0 (131) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15,18-dimethyl-20-nor-11a -carbathromb-5Z-enoic acid, PA0 (132) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16,17-dimethyl-20-nor-11a -carbathromb-5Z-enoic acid, PA0 (133) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16,18-dimethyl-20-nor-11a -carbathromb-5Z-enoic acid, PA0 (134) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-17,18-dimethyl-20-nor-11a -carbathromb-5Z-enoic acid, PA0 (135) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15,16-dimethyl-11a-carbat hromb-5Z-enoic acid, PA0 (136) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15,17-dimethyl-11a-carbat hromb-5Z-enoic acid, PA0 (137) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15,18-dimethyl-11a-carbat hromb-5Z-enoic acid, PA0 (138) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo- 15,19-dimethyl-11a-carbathromb-5Z-enoic acid, PA0 (139) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16,17-dimethyl-11a-carbat hromb-5Z-enoic acid, PA0 (140) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16,18-dimethyl-11a-carbat hromb-5Z-enoic acid, PA0 (141) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16,19-dimethyl-11a-carbat hromb-5Z-enoic acid, PA0 (142) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-17,18-dimethyl-11a-carbat hromb-5Z-enoic acid, PA0 (143) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-17,19-dimethyl-11a-carbat hromb-5Z-enoic acid, PA0 (144) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-18,19-dimethyl-11a-carbat hromb-5Z-enoic acid, PA0 (145) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15,15-dimethyl-18,19,20-t rinor-11a-carbathromb-5Z-enoic acid, PA0 (146) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15,15-dimethyl-19,20-dino r-11a-carbathromb-5Z-enoic acid, PA0 (147) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16,16-dimethyl-19,20-dino r- 11a-carbathromb-5Z-enoic acid, PA0 (148) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15,15-dimethyl-20-nor-11a -carbathromb-5Z-enoic acid, PA0 (149) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16,16-dimethyl-20-nor-11a -carbathromb-5Z-enoic acid, PA0 (150) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-17,17-dimethyl-20-nor-11a -carbathromb-5Z-enoic acid, PA0 (151) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15,15-dimethyl-11a-carbat hromb-5Z-enoic acid, PA0 (152) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16,16-dimethyl-11a-carbat hromb-5Z-enoic acid, PA0 (153) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-17,17-dimethyl-11a-carbat hromb-5Z-enoic acid, PA0 (154) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-18,18-dimethyl-11a-carbat hromb-5Z-enoic acid, PA0 (155) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15,15-dimethyl-20-nor-11a -carbathromb-5Z-en-17-ynoic acid, PA0 (156) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15,15-dimethyl-11a-carbat hromb-5Z-en-17-ynoic acid, PA0 (157) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16,16-dimethyl-11a-carbat hromb-5Z-en-17-ynoic acid, PA0 (158) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16,20,20-trimethyl-11a-ca rbathromb-5Z,19-dienoic acid, PA0 (159) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16,19-dimethyl-11a-carbat hromb-5Z,18-dienoic acid, PA0 (160) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16,18-dimethyl-20-nor-11a -carbathromb-5Z,17-dienoic acid, PA0 (161) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-14-cyclopentyl-15,16,17,1 8,19,20-hexanor-11a-carbathromb-5Z-enoic acid, PA0 (162) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-14-(3-propylcyclopentyl)- 15,16,17,18,19,20-hexanor-11a-carbathromb-5Z-enoic acid, PA0 (163) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-14-(3-butylcyclopentyl)-1 5,16,17,18,19,20-hexanor-11a-carbathromb-5Z-enoic acid, PA0 (164) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-cyclopentyl-16,17,18,1 9,20-pentanor-11a-carbathromb-5Z-enoic acid, PA0 (165) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-(3-propylcyclopentyl)- 16,17,18,19,20-pentanor-11a-carbathromb-5Z-enoic acid, PA0 (166) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo- 15-(3-butylcyclopentyl)-16,17,18,19,20-pentanor-11a-carbathromb-5Z-enoic acid, PA0 (167) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-cyclopentyl-17,18,19,2 0-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (168) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-(3-propylcyclopentyl)- 17,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (169) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-(3-butylcyclopentyl)-1 7,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (170) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-cyclopentylthio-16,17, 18,99,20-pentanor-11a-carbathromb-5Z-enoic acid, PA0 (171) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-(3-propylcyclopentylth io)-16,17,18,19,20-pentanor-11a-carbathromb-5Z-enoic acid, PA0 (172) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-(3-butylcyclopentylthi o)-16,17,18,19,20-pentanor-11a-carbathromb-5Z-enoic acid, PA0 (173) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-cyclopentylthio-17,18, 19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (174) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-(3-propylcyclopentylth io)-17,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (175) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-(3-butylcyclopentylthi o)-17,18,19,20-tetranor- 11a-carbathromb-5Z-enoic acid, PA0 (176) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-17-cyclopentylthio-18,19, 20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (177) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-17-(3-propylcyclopentylth io)-18,19,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (178) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-17-(3-butylcyclopentylthi o)-18,19,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (179) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-cyclopentyloxy-16,17,1 8,19,20-pentanor-11a-carbathromb-5Z-enoic acid, PA0 (180) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-(3-propylcyclopentylox y)-16,17,18,19,20-pentanor-11a-carbathromb-5Z-enoic acid, PA0 (181) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-(3-butylcyclopentyloxy )-16,17,18,19,20-pentanor-11a-carbathromb-5Z-enoic acid, PA0 (182) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-cyclopentyloxy-16,17,1 8,19,20-pentanor-11a-carbathromb-5Z-enoic acid, PA0 (183) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-(3-propylcyclopentylox y)-16,17,18,19,20-pentanor-11a-carbathromb-5Z-enoic acid, PA0 (184) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-(3-butylcyclopentyloxy )-16,17,18,19,20-pentanor-11a-carbathromb-5Z-enoic acid, PA0 (185) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-methyl-16-cyclopentyl- 17,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (186) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-methyl-16-(3-propylcyc lopentyl)-17,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (187) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-methyl-16-(3-butylcycl opentyl)-17,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (188) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-17-methyl-17-cyclopentyl- 18,19,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (189) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-17-methyl-17-(3-propylcyc lopentyl)-18,19,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (190) 90.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-17-methyl-17-(3-butylcyc lopentyl)-18,19,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (191) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-methyl-17-cyclopentyl- 18,19,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (192) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-methyl-17-(3-propylcyc lopentyl)-18,19,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (193) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-methyl-17-(3-butylcycl opentyl)-18,19,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (194) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo- 14-(1-hydroxycyclopentyl)-15,16,17,18,19,20-pentanor-11a-carbathromb-5Z-en oic acid, PA0 (195) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-14-(1-hydroxy-3-propylcyc lopentyl)-15,16,17,18,19,20-pentanor-11a-carbathromb-5Z-enoic acid, PA0 (196) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-14-(1-hydroxy-3-butylcycl opentyl)-15,16,17,18,19,20-pentanor-11a-carbathromb-5Z-enoic acid, PA0 (197) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-17-cyclopentyl-18,19,20-t rinor-11a-carbathromb-5Z-enoic acid, PA0 (198) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-17-(3-propylcyclopentyl)- 18,19,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (199) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-17-(3-butylcyclopentyl)-1 8,19,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (200) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-cyclopentyl-17,18,19,2 0-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (201) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-(3-propylcyclopentyl)- 17,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (202) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-(3-butylcyclopentyl)-1 7,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (203) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15,15-dimethyl-16-cyclope ntyl-17,18,19,20-tetranor- 11a-carbathromb-5Z-enoic acid, PA0 (204) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15,15-dimethyl-16-(3-prop ylcyclopentyl)-17,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (205) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15,15-dimethyl-16-(3-buty lcyclopentyl)-17,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (206) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16,16-dimethyl-16-cyclope ntyl-17,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (207) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16,16-dimethyl-16-(3-prop ylcyclopentyl)-17,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (208) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16,16-dimethyl-16-(3-buty lcyclopentyl)-17,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (209) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-cyclohexyl-17,18,19,20 -tetranor-11a-carbathromb-5Z-enoic acid, PA0 (210) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-(4-propylcyclohexyl)-1 7,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (211) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-(4-butylcyclohexyl)-17 ,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (212) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-17-cyclohexyl-18,19,20-tr inor-11a-carbathromb-5Z-enoic acid, PA0 (213) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-17-(4-propylcyclohexyl)-1 8,19,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (214) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-17-(4-butylcyclohexyl)-18 ,19,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (215) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-(2-naphthyl)-16,17,18, 19,20-pentanor-11a-carbathromb-5Z-enoic acid, PA0 (216) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-(2-naphthyl)-17,18,19, 20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (217) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-17-(2-naphthyl)-18,19,20- trinor-11a-carbathromb-5Z-enoic acid, PA0 (218) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-(3-indolyl)-16,17,18,1 9,20-pentanor-11a-carbathromb-5Z-enoic acid, PA0 (219) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-(3-indolyl)-17,18,19,2 0-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (220) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-17-(3-indolyl)-88,19,20-t rinor-11a-carbathromb-5Z-enoic acid, PA0 (221) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-(2-indanyl)-16,17,18,1 9,20-pentanor-11a-carbathromb-5Z-enoic acid, PA0 (222) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo- 16-(2-indanyl)-17,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (223) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-17-(2-indanyl)-18,19,20-t rinor-11a-carbathromb-5Z-enoic acid, PA0 (224) 9.alpha.,11.alpha.-dimethylmethano13,15-diaza-14-oxo-20-nor-11a-carbathrom b-5Z-enoic acid, PA0 (225) 9.alpha.,11.alpha.-dimethylmethano-13,15-diaza-14-oxo-19,20-dinor-11a-carb athromb-5Z-enoic acid, PA0 (226) 9.alpha.,11.alpha.-dimethylmethano-13,15-diaza-14-oxo-18,19,20-trinor-11a- carbathromb-5Z-enoic acid, PA0 (227) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-hydroxy-16-phenyl-17,1 8,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (228) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-hydroxy-16-(4-methylph enyl)-17,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (229) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-hydroxy-16-(4-propylph enyl)-17,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (230) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-hydroxy-16-(4-butylphe nyl)-17,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (231) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-hydroxy-16-(4-methoxyp henyl)-17,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (232) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-hydroxy-16-(3-chloroph enyl)-17,18,19,20-tetranor- 11a-carbathromb-5Z-enoic acid, PA0 (233) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-hydroxy-17-phenyl-18,1 9,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (234) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-hydroxy-17-(4-methylph enyl)-18,19,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (235) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-hydroxy-17-(4-propylph enyl)-18,19,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (236) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-hydroxy-17-(4-butylphe nyl)-18,19,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (237) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-hydroxy-17-(4-methoxyp henyl)-18,19,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (238) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-hydroxy-17-(3-chloroph enyl)-18,19,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (239) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-amino-16-phenyl-17,18, 19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (240) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-amino-16-(4-methylphen yl)-17,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (241) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-amino-16-(4-propylphen yl)-17,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (242) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-amino-16-(4-butylpheny l)-17,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (243) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-amino-16-(4-methoxyphe nyl)-17,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (244) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-amino-16-(3-chlorophen yl)-17,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (245) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-hydroxy-17,18,19,20-te tranor-11a-carbathromb-5Z-enoic acid, PA0 (246) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-hydroxy-18,19,20-trino r-11a-carbathromb-5Z-enoic acid, PA0 (247) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-hydroxy-19,20-dinor-11 a-carbathromb-5Z-enoic acid, PA0 (248) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-hydroxy-20-nor-11a-car bathromb-5Z-enoic acid, PA0 (249) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-hydroxy-11a-carbathrom b-5Z-enoic acid, PA0 (250) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-hydroxy-20-methyl-11a- carbathromb-5Z-enoic acid, PA0 (251) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-hydroxy-16-methyl-18,1 9,20-trinor- 11a-carbathromb-5Z-enoic acid, PA0 (252) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-hydroxy-17-methyl-19,2 0-dinor-11a-carbathromb-5Z-enoic acid, PA0 (253) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-hydroxy-18-methyl-20-n or-11a-carbathromb-5Z-enoic acid, PA0 (254) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-hydroxy-19-methyl-11a- carbathromb-5Z-enoic acid, PA0 (255) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-hydroxy-20,20-dimethyl -11a-carbathromb-5Z-enoic acid, PA0 (256) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-hydroxy-16-methyl-19,2 0-dinor-11a-carbathromb-5Z-enoic acid, PA0 (257) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-hydroxy-16-methyl-20-n or-11a-carbathromb-5Z-enoic acid, PA0 (258) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-hydroxy-16-methyl-11a- carbathromb-5Z-enoic acid, PA0 (259) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-hydroxy-16,20-dimethyl -11a-carbathromb-5Z-enoic acid, PA0 (260) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-hydroxy-17-methyl-20-n or-11a-carbathromb-5Z-enoic acid, PA0 (261) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-hydroxy-17-methyl-11a- carbathromb-5Z-enoic acid, PA0 (262) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-hydroxy-17,20-dimethyl -11a-carbathromb-5Z-enoic acid, PA0 (263) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-hydroxy-18-methyl-11a- carbathromb-5Z-enoic acid, PA0 (264) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-hydroxy-18,20-dimethyl -11a-carbathromb-5Z-enoic acid, PA0 (265) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-hydroxy-19,20-dimethyl -11a-carbathromb-5Z-enoic acid, PA0 (266) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-hydroxy-15-cyclopentyl -16,17,18,19,20-pentanor-11a-carbathromb-5Z-enoic acid, PA0 (267) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-hydroxy-15-(3-propylcy clopentyl)-16,17,18,19,20-pentanor-11a-carbathromb-5Z-enoic acid PA0 (268) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-hydroxy-15-(3-butylcyc lopentyl)-16,17,18,19,20-pentanor-11a-carbathromb-5Z-enoic acid, PA0 (269) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-chloro-15-cyclopentyl- 16,17,18,19,20-pentanor-11a-carbathromb-5Z-enoic acid, PA0 (270) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo- 15-chloro-15-(3-propylcyclopentyl)-16,17,18,19,20-pentanor-11a-carbathromb -5Z-enoic acid, PA0 (271) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-chloro-15-(3-butylcycl opentyl)-16,17,18,19,20-pentanor-11a-carbathromb-5Z-enoic acid, PA0 (272) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-phenylthio-15-cyclopen tyl-16,17,18,19,20-pentanor-11a-carbathromb-5Z-enoic acid, PA0 (273) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-phenylthio-15-(3-propy lcyclopentyl)-16,17,18,19,20-pentanor-11a-carbathromb-5Z-enoic acid, PA0 (274) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-phenylthio-15-(3-butyl cyclopentyl)-16,17,18,19,20-pentanor-11a-carbathromb-5Z-enoic acid, PA0 (275) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-hydroxy-16-cyclopentyl -17,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (276) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-hydroxy-16-(3-propylcy clopentyl)-17,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (277) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-hydroxy-16-(3-butylcyc lopentyl)-17,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (278) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-chloro-16-cyclopentyl- 17,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (279) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-chloro-16-(3-propylcyc lopentyl)-17,18,19,20-tetranor- 11a-carbathromb-5Z-enoic acid, PA0 (280) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-chloro-16-(3-butylcycl opentyl)-17,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (281) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16phenylthio-16-cyclopent yl-17,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (282)-9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-phenylthio-16-(3- propylcyclopentyl)-17,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (283) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-phenylthio-16-(3-butyl cyclopentyl)-17,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (284) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-hydroxy-17-cyclopentyl -18,19,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (285) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-hydroxy-17-(3-propylcy clopentyl)-18,19,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (286) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-hydroxy-17-(3-butylcyc lopentyl)-18,19,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (287) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-chloro-17-cyclopentyl- 18,19,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (288) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-chloro-17-(3-propylcyc lopentyl)-18,19,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (289) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-chloro-17-(3-butylcycl opentyl)-18,19,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (290) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-phenylthio-17-cyclopen tyl-18,19,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (291) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-phenylthio-17-(3-propy lcyclopentyl)-18,19,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (292) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-phenylthio-17-(3-butyl cyclopentyl)-18,19,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (293) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-hydroxy-15-cyclohexyl- 16,17,18,19,20-pentanor-11a-carbathromb-5Z-enoic acid, PA0 (294) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-hydroxy-15-(4-propylcy clohexyl)-16,17,18,19,20-pentanor-11a-carbathromb-5Z-enoic acid, PA0 (295) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-hydroxy-15-(4-butylcyc lohexyl)-16,17,18,19,20-pentanor-11a-carbathromb-5Z-enoic acid, PA0 (296) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-chloro-15-cyclohexyl-1 6,17,18,19,20-pentanor-11a-carbathromb-5Z-enoic acid, PA0 (297) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-chloro-15-(4-propylcyc lohexyl)-16,17,18,19,20-pentanor-11a-carbathromb-5Z-enoic acid, PA0 (298) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo- 15-chloro-15-(4-butylcyclohexyl)-16,17,18,19,20-pentanor-11a-carbathromb-5 Z-enoic acid, PA0 (299) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-phenylthio-15-cyclohex yl-16,17,18,19,20-pentanor-11a-carbathromb-5Z-enoic acid, PA0 (300) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-phenylthio-15-(4-propy lcyclohexyl)-16,17,18,19,20-pentanor-11a-carbathromb-5Z-enoic acid, PA0 (301) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-phenylthio-15-(4-butyl cyclohexyl)-16,17,18,19,20-pentanor-11a-carbathromb-5Z-enoic acid, PA0 (302) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-hydroxy-16-cyclohexyl- 17,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (303) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-hydroxy-16-(4-propylcy clohexyl)-17,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (304) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-hydroxy-16-(4-butylcyc lohexyl)-17,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (305) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-chloro-16-cyclohexyl-1 7,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (306) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-chloro-16-(4-propylcyc lohexyl)-17,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (307) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-chloro-16-(4-butylcycl ohexyl)-17,18,19,20-tetranor- 11a-carbathromb-5Z-enoic acid, PA0 (308) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-phenylthio-16-cyclohex yl-17,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (309) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-phenylthio-16-(4-propy lcyclohexyl)-17,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (310) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-phenylthio-16-(4-butyl cyclohexyl)-17,18,19,20-tetranor-11a-carbathromb-5Z-enoic acid, PA0 (311) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-hydroxy-17-cyclohexyl- 18,19,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (312) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-hydroxy-17-(4-propylcy clohexyl)-18,19,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (313) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-hydroxy-17-(4-butylcyc lohexyl)-18,19,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (314) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-chloro-17-cyclohexyl-1 8,19,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (315) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-chloro-17-(4-propylcyc lohexyl)-18,19,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (316) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-15-chloro-17-(4-butylcycl ohexyl)-18,19,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (317) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-phenylthio-17-cyclohex yl-18,19,20-trinor-11a-carbathromb-5Z-enoic acid, PA0 (318) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-phenylthio-17-(4-propy lcyclohexyl)-18,19,20-trinor-11a-carbathromb-5Z-enoic acid and PA0 (319) 9.alpha.,11.alpha.-dimethylmethano-13-aza-14-oxo-16-phenylthio-17-(4-butyl cyclohexyl)-18,19,20-trinor-11a-carbathromb-5Z-enoic acid; and esters thereof
With proviso that, R.sup.50 should not be an alkoxy, alkylthio, cycloalkyloxy or cycloalkylthio group, when R.sup.30 represent a hydroxy group and R.sup.4 represents a bond.]